Title: Forced and natural carbonation of lime-based mortars with and without additives: Mineralogical and textural changes

Abstract

We have studied the carbonation process in different types of mortars, with and without pozzolana or air-entraining additives, subject to a CO{sub 2}-rich atmosphere and compared the results with those of similar naturally carbonated mortars. We used X-ray diffraction technique to demonstrate that high CO{sub 2} concentrations favour a faster, more complete carbonation process with 8 days being sufficient to convert portlandite into 90 wt.% calcite. Full carbonation, however, is not reached during the life-span of the tests, not even in forced carbonation experiments. This could be due to at least one of the following phenomena: a premature drying of samples during carbonation reaction, the temperature at which the carbonation process was carried out or the reduction of pore volume occupied by newly formed calcite crystals. This last option seems to be the least probable. We observed a more prolific development of calcite crystals in the pores and fissures through which the carbonic anhydride flows. Under natural conditions, carbonation is much slower and similar levels are not reached for 6 months. These differences suggest that the carbonation process is influenced by the amount of CO{sub 2} used. Both the mineralogy and texture of mortars vary depending on the type ofmore » additive used but the speed of the portlandite-calcite transformation does not change significantly. Pozzolana produces hydraulic mortars although the quantity of calcium aluminosilicate crystals is low. The air-entraining agent significantly alters the texture of the mortars creating rounded pores and eliminating or reducing the drying cracks.« less

@article{osti_20793259,
title = {Forced and natural carbonation of lime-based mortars with and without additives: Mineralogical and textural changes},
author = {Cultrone, G. and Sebastian, E. and Huertas, M. Ortega},
abstractNote = {We have studied the carbonation process in different types of mortars, with and without pozzolana or air-entraining additives, subject to a CO{sub 2}-rich atmosphere and compared the results with those of similar naturally carbonated mortars. We used X-ray diffraction technique to demonstrate that high CO{sub 2} concentrations favour a faster, more complete carbonation process with 8 days being sufficient to convert portlandite into 90 wt.% calcite. Full carbonation, however, is not reached during the life-span of the tests, not even in forced carbonation experiments. This could be due to at least one of the following phenomena: a premature drying of samples during carbonation reaction, the temperature at which the carbonation process was carried out or the reduction of pore volume occupied by newly formed calcite crystals. This last option seems to be the least probable. We observed a more prolific development of calcite crystals in the pores and fissures through which the carbonic anhydride flows. Under natural conditions, carbonation is much slower and similar levels are not reached for 6 months. These differences suggest that the carbonation process is influenced by the amount of CO{sub 2} used. Both the mineralogy and texture of mortars vary depending on the type of additive used but the speed of the portlandite-calcite transformation does not change significantly. Pozzolana produces hydraulic mortars although the quantity of calcium aluminosilicate crystals is low. The air-entraining agent significantly alters the texture of the mortars creating rounded pores and eliminating or reducing the drying cracks.},
doi = {10.1016/J.CEMCONRES.2004.1},
journal = {Cement and Concrete Research},
number = 12,
volume = 35,
place = {United States},
year = {Thu Dec 15 00:00:00 EST 2005},
month = {Thu Dec 15 00:00:00 EST 2005}
}

The pore structures of carbonated non-hydraulic lime mortars made with a range of different aggregates and concentrations of lime have been determined using mercury intrusion porosimetry (MIP). MIP data have been correlated with scanning electron microscopy images and other porosity data. During carbonation there is an increase in pore volume in the {approx} 0.1 {mu}m pore diameter range across all mortar types which is attributed to the transformation of portlandite to calcite. Also there is a monotonic increase in the volumes of pores with diameters below 0.03 {mu}m. A model is proposed for the changes in pore structure caused bymore » carbonation. This attributes the increase in the volume of sub 0.03 {mu}m pores to the attachment of calcite crystals to the surface of aggregate particles, and in some cases to the surface of portlandite crystals. This phenomenon may explain the continuing presence of portlandite in mortars that, apparently, have fully carbonated.« less

Highlights: > Accelerated carbonation studied to improve environmental properties of steel slag. > Carbonation found to occur predominantly at surface of the steel slag grains. > Combined geochemical modelling and mineral analysis revealed controlling processes. > Enhanced V-leaching with di-Ca silicate (C2S) dissolution identified as major source. > Identified mineral transformations provide guidance for further quality improvement. - Abstract: Steel slag can be applied as substitute for natural aggregates in construction applications. The material imposes a high pH (typically 12.5) and low redox potential (Eh), which may lead to environmental problems in specific application scenarios. The aim of this studymore » is to investigate the potential of accelerated steel slag carbonation, at relatively low pCO{sub 2} pressure (0.2 bar), to improve the environmental pH and the leaching properties of steel slag, with specific focus on the leaching of vanadium. Carbonation experiments are performed in laboratory columns with steel slag under water-saturated and -unsaturated conditions and temperatures between 5 and 90 {sup o}C. Two types of steel slag are tested; free lime containing (K3) slag and K1 slag with a very low free lime content. The fresh and carbonated slag samples are investigated using a combination of leaching experiments, geochemical modelling of leaching mechanisms and microscopic/mineralogical analysis, in order to identify the major processes that control the slag pH and resulting V leaching. The major changes in the amount of sequestered CO{sub 2} and the resulting pH reduction occurred within 24 h, the free lime containing slag (K3-slag) being more prone to carbonation than the slag with lower free lime content (K1-slag). While carbonation at these conditions was found to occur predominantly at the surface of the slag grains, the formation of cracks was observed in carbonated K3 slag, suggesting that free lime in the interior of slag grains had also reacted. The pH of the K3 slag (originally pH {+-} 12.5) was reduced by about 1.5 units, while the K1 slag showed a smaller decrease in pH from about 11.7 to 11.1. However, the pH reduction after carbonation of the K3 slag was observed to lead to an increased V-leaching. Vanadium leaching from the K1 slag resulted in levels above the limit values of the Dutch Soil Quality Decree, for both the untreated and carbonated slag. V-leaching from the carbonated K3 slag remained below these limit values at the relatively high pH that remained after carbonation. The V-bearing di-Ca silicate (C2S) phase has been identified as the major source of the V-leaching. It is shown that the dissolution of this mineral is limited in fresh steel slag, but strongly enhanced by carbonation, which causes the observed enhanced release of V from the K3 slag. The obtained insights in the mineral transformation reactions and their effect on pH and V-leaching provide guidance for further improvement of an accelerated carbonation technology.« less

Studies monitoring the carbonation of NHL3.5 hydraulic lime are described. Weight-gain measurements, focused ion beam imaging, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy were used to monitor changes in structure and composition occurring in lime pastes after exposure to 100% carbon dioxide at relative humidities of 65 and 97%. Lime paste exposed to a relative humidity (R.H.) of 97% indicated a higher carbonation rate compared to paste exposed to 65% R.H. Surface analysis showed that the sample exposed to a relative humidity of 97% was completely carbonated. No calcium hydroxide was detected. A small amount of calcium hydroxide was,more » however, present at the surface of the sample exposed to 65% R.H. These observations suggest that high humidity results in the formation of a thin layer of crystalline calcium carbonate covering silicate and hydroxide phases. The actual mass increase of the sample also indicated that uncarbonated calcium hydroxide remained beneath the surface.« less

The increasing use of lime-based mortars for the restoration of historic buildings and structures justifies the research on these materials. The focus of this paper is the effect of technological variables on pore structure and mechanical properties of lime-based mortars. The influence of curing time, binder-aggregate (B/Ag) ratio, aggregate attributes and porosity is discussed. Mortars prepared with aerial lime, varying aggregate types and B/Ag ratios ranging from 1:1 to 1:5 by volume were tested. Compressive and flexural strength measurements, as well as X-ray diffraction (XRD) and thermal studies, were performed after 3, 7, 28, 91, 182 and 365 days. Amore » strong increase in strength of mortar mixtures after 365 curing days (as compared to 28 curing days) is found. In spite of the fact that larger amounts of binder increase the total porosity, the strength of these mixtures is also increased. A good interlocked structure is obtained as binder contents increase. Also, higher porosities allow better portlandite carbonation. A relationship between mechanical properties and pore structure was established. However, in case of binder excess, the increase in voids leads to a strength reduction. The use of calcareous aggregates improves strength more as compared to the use of siliceous aggregates. Factors as grain size distribution and grain shape of the aggregates have also been considered.« less

The main focus of this work is to determine the effect of cement addition, a common practice in many restorations, on the pore structure of lime-based mortars. A second target is to establish correlations between microstructure and water vapor transport across the mortar, which is a key characteristic of building decay. In order to achieve these objectives, we prepared a set of mortars consisting of air-hardening lime with a progressively increasing cement content, as well as a mortar containing hydraulic lime. Several different techniques, most notably mercury intrusion porosimetry and scanning electron microscopy in the backscatter mode, were used tomore » investigate the pore structure. The results from these procedures led to the conclusion that porosity and pore size are progressively reduced as cement content increases. Moreover, an excellent correlation between pore radius parameter and the vapor diffusion coefficient was established. Hydraulic lime mortar exhibited textural parameters and diffusivity values halfway between those of the different lime/cement mixes studied.« less